US7361213B2 - Borazine-boron nitride hybrid hydrogen storage system - Google Patents
Borazine-boron nitride hybrid hydrogen storage system Download PDFInfo
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- US7361213B2 US7361213B2 US11/208,816 US20881605A US7361213B2 US 7361213 B2 US7361213 B2 US 7361213B2 US 20881605 A US20881605 A US 20881605A US 7361213 B2 US7361213 B2 US 7361213B2
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- hydrogen storage
- hydrogen
- borazine
- borazane
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- 0 CNB(N*(N*Cl)Cl)Cl Chemical compound CNB(N*(N*Cl)Cl)Cl 0.000 description 3
- DXGYEQLHEHARDM-AOZJVWGDSA-N B.B.BNC.BNC.BNC.C1CCOC1.CN.CN.[2HH].[H]C Chemical compound B.B.BNC.BNC.BNC.C1CCOC1.CN.CN.[2HH].[H]C DXGYEQLHEHARDM-AOZJVWGDSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N C1CCCCC1 Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- JUTRDZVOQBPYBG-UHFFFAOYSA-N C[BH](NBC(C)(CCCC)CCCC)NBNC Chemical compound C[BH](NBC(C)(CCCC)CCCC)NBNC JUTRDZVOQBPYBG-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
- C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B6/00—Hydrides of metals including fully or partially hydrided metals, alloys or intermetallic compounds ; Compounds containing at least one metal-hydrogen bond, e.g. (GeH3)2S, SiH GeH; Monoborane or diborane; Addition complexes thereof
- C01B6/06—Hydrides of aluminium, gallium, indium, thallium, germanium, tin, lead, arsenic, antimony, bismuth or polonium; Monoborane; Diborane; Addition complexes thereof
- C01B6/10—Monoborane; Diborane; Addition complexes thereof
- C01B6/13—Addition complexes of monoborane or diborane, e.g. with phosphine, arsine or hydrazine
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/32—Hydrogen storage
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S502/00—Catalyst, solid sorbent, or support therefor: product or process of making
- Y10S502/526—Sorbent for fluid storage, other than an alloy for hydrogen storage
Definitions
- the present invention relates to systems for storing hydrogen, and more particularly to hybrid systems for storing hydrogen that use a borazine-boron nitride composite system wherein the borazine component stores hydrogen in combined form as a hydride and wherein boron nitride component stores hydrogen by physisorption.
- Hydrogen is well known as one of the cleanest of available fuels because it can be reacted with oxygen to produce energy and water in hydrogen-consuming devices such as fuel cell and internal combustion engines, for example. Virtually no other reaction byproducts are produced in the exhaust, thereby avoiding well established environmental hazards associated with the use of petroleum based fuels.
- Safe and efficient storage of hydrogen is essential for hydrogen-consuming applications.
- important factors involved in the development of mobile hydrogen-consuming applications include minimization of volume and weight of the hydrogen storage systems, while maximizing the safety thereof.
- An alternative is to store hydrogen under high pressure in cylinders.
- a 100 pound steel cylinder can only store about one pound of hydrogen at about 2200 psi, which translates into 1% by weight of hydrogen storage.
- More expensive composite cylinders with special compressors can store hydrogen at higher pressures of about 4,500 psi to achieve a more favorable storage ratio of about 4% by weight.
- safety factors and the large amount of energy consumed in achieving such high pressures have compelled a search for alternative hydrogen storage technologies that are both safe and efficient.
- objects of the present invention include: systems and methods that enable effective, safe, efficient storage, and controllable release of hydrogen, especially for energetic systems such as fuel cells and the like; a hydrogen storage system that provides an initial release of hydrogen for initial operation of a hydrogen-consuming process and subsequent “on-demand” release of hydrogen for ongoing operation of the hydrogen-consuming process. Further and other objects of the present invention will become apparent from the description contained herein.
- a hybrid hydrogen storage composition that includes a first phase and a second phase adsorbed on the first phase, the first phase including boron nitride for storing hydrogen by physisorption and the second phase including a borazane-borazine system for storing hydrogen in combined form as a hydride.
- a hydrogen storage system includes a containment vessel containing a hybrid hydrogen storage composition including a first phase and a second phase adsorbed on the first phase, the first phase comprising BN for storing hydrogen by physisorption and the second phase comprising a borazane-borazine system for storing hydrogen in combined form as a hydride.
- FIG. 1 is a schematic molecular diagram of a borazane-borazine cyclic system in accordance with the present invention.
- FIG. 2 a is a schematic molecular diagram of a borazine polymer.
- FIG. 2 b is a schematic molecular diagram of a borazane polymer.
- FIG. 3 a is a schematic molecular diagram phenalene borazine analogue.
- FIG. 3 b is a schematic molecular diagram biphenyl borazine analogue.
- FIG. 3 c is a schematic molecular diagram naphthalene borazine analogue.
- FIG. 4 is a schematic, not-to-scale illustration of an embodiment of the invention that involves a detachable cartridge containing the composite materials of the present invention.
- the present invention involves a hybrid storage system incorporating both hydrogen sorption and chemical-hydride storage media.
- the present invention involves a new class of composite materials comprising low-molecular weight boron-nitrogen compounds, particularly a borazane/borazane polymer system, impregnated (sorbed) into high-surface area boron nitride (BN).
- Hydrogen sorption media makes low-pressure hydrogen available during start-up of a vehicle while chemical-hydride media releases hydrogen “on-demand” during vehicle operation.
- the borazane molecule contains 13.9 wt. % hydrogen and can release 6.9 wt. % of the hydrogen via a borazane-borazine chemical transformation.
- High surface area BN powders can store and release ⁇ 2 wt. % hydrogen.
- the hydrogen storage limits for this system are approximately 2-6.9% (0% borazane to 0% BN) at low temperatures. Since the density of borazane is 0.96 ⁇ 0.01 g/cm 3 , the volumetric hydrogen storage is not significantly different.
- Borazane, B 3 N 3 H 12 which is the B—N analogue of cyclohexane, can undergo facile chemical hydrogenation-dehydrogenation. It is known that borazane can be prepared from hydrochlorination and sodium borohydride reduction of borazine, B 3 N 3 H 6 ., and that borazane reverts to borazine on heating at 200° C. However, such a system has limitations that there is no hydrogen available for start-up of vehicle and external energy is needed to initiate release of hydrogen from borazane to start the vehicles.
- the hydrogenation-dehydrogenation pathway of the borazane-borazine system operates as follows:
- the borazane-borazine system includes borazine polymers because they can also be subjected to hydrochlorination and reduction for hydrogen storage because the reaction chemistry will occur on the borazine rings.
- a simple borazine polymer shown in FIG. 2 a , can be synthesized directly from B-trichloroborazine and hexamethyldisilazane.
- FIG. 2 b shows the borazane polymer produced upon hydrogenation.
- Such borazane polymer will contain ⁇ 12.9 wt. % hydrogen and will release ⁇ 6 wt. % hydrogen during low temperature dehydrogenation.
- complex polymeric borazine analogues are suitable for use in hydrogenation-dehydrogenation cycles, including, but not limited to phenalene, biphenyl, and naphthalene analogues.
- Complex polymeric borazane-borazine systems impregnated on high-surface area BN can alleviate potential gas-separation issues that may be present in simple borazane/BN composites.
- the polymeric systems are solids in both hydrogenated (borazane) and dehydrogenated (borazine) form and do not have any inherent problems associated with the use of volatile liquids for hydrogen storage.
- Trimethylborazanes used in the testing of the present invention had been stored in screw cap bottles for approximately 20 years.
- borazane-impregnated BN is viable hydrogen storage system. Moreover, high-surface-area BN is used as a borazane carrier as well as a borazine adsorber.
- the polymeric chemical hydride system overcomes the inherent problems associated with the use of volatile liquids for hydrogen storage. Moreover, the chemical hydride component can be hydrogenated by chemical reactions routes such as, but not limited to, hydrochlorination and reduction. Hydrogenation and dehydrogenation can be facilitated at low temperatures by use of a catalyst system.
- This system retains most of the hydrogen storage capacity ( ⁇ 6.0%), but the primary advantage thereof is that media remain in solid state through hydrogenation-dehydrogenation cycle. This eliminates the need to separate hydrogen from volatile dehydrogenated borazane (i.e., borazine).
- the decomposition temperature of trimethylcycloborazane was determined to be 250° C. at atmospheric pressure. [CH 3 N(H)BH 2 ] 3 ⁇ [CH 3 NBH] 3 +3H 2
- the model compound released 4.49% H 2 at 80° C. and additional 4.7% H 2 at 260° C. (w/w ⁇ v/v since density is ⁇ 1).
- the model compound was dissolved in organic solvents (such as, but not limited to, benzene, tetrahydrofuran etc.) and impregnated into high-surface-area BN.
- BN particulates can be used, high-surface-area BN is preferred for use in carrying out the present invention because the available surface area is directly proportional to the amount of borazane and/or borazine that can be loaded (sorbed) thereon. Although lesser loadings are operable in carrying out the present invention, the preferred loading of borazane and/or borazine is the maximum amount of borazane and/or borazine that can be loaded onto the BN, i.e. saturation.
- Spherical, high-surface-area BN particles were prepared in two steps in accordance with U.S. Pat. No. 6,348,179 issued on Feb. 19, 2002 to Paine, et al.
- a conventional aerosol reactor was used with commercially available trialkylborate compounds and ammonia to form BN x O y spherical particles with oxygen levels less than 8 wt %.
- Brief calcination of the particles in NH 3 gave smooth spherical morphology particles of BN.
- At least one catalyst can be added in an amount in the range of about 0.05 wt % to about 1%, preferably about 0.5% to about 0.8%. Too little catalyst can be ineffective, and too much catalyst would not be cost-effective.
- Catalytic dehydrogenation reduces the temperature of dehydrogenation and the complexity associated with chemical hydrogenation protocol.
- the catalyzed dehydrogenative coupling of >B—H bond with >N—H bond can be adapted for dehydrogenation of —[H 2 B-—NH 2 ]— bonds.
- compositions of the present invention can be encapsulated in a containment vessel for storing hydrogen.
- a versatile embodiment of the invention is shown in FIG. 4 .
- a detachable cartridge 40 containing the composite materials of the present invention 44 (viewed through cutaway 42 ) that can be integrated into fuel systems.
- a spent cartridge 40 can be replaced and/or refueled at a refueling station 50 by means of a valve 46 or other conventional means.
- a fresh cartridge 40 is mounted in a vehicle 52 where the hydrogen is used to power the vehicle 52 in accordance with the present invention.
- Spent cartridges can alternatively be taken to a central facility for recharging (hydrogenation) in accordance with the present invention.
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- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Filling Or Discharging Of Gas Storage Vessels (AREA)
- Hydrogen, Water And Hydrids (AREA)
Abstract
Description
[CH3N(H)BH2]3→[CH3NBH]3 +3H2
Claims (11)
Priority Applications (1)
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US11/208,816 US7361213B2 (en) | 2005-08-22 | 2005-08-22 | Borazine-boron nitride hybrid hydrogen storage system |
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US11/208,816 US7361213B2 (en) | 2005-08-22 | 2005-08-22 | Borazine-boron nitride hybrid hydrogen storage system |
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US20070039474A1 US20070039474A1 (en) | 2007-02-22 |
US7361213B2 true US7361213B2 (en) | 2008-04-22 |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20110008693A1 (en) * | 2009-07-08 | 2011-01-13 | Ford Motor Company | Hydrogen storage materials containing ammonia borane |
US8029602B1 (en) * | 2009-03-05 | 2011-10-04 | The United States Of America As Represented By The Secretary Of The Navy | Chemical hydrogen storage materials having guanidinium borohydride |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2006132292A1 (en) * | 2005-06-06 | 2006-12-14 | Nippon Oil Corporation | Porous substance and process for production thereof |
US7544837B2 (en) * | 2005-11-04 | 2009-06-09 | Los Alamos National Security, Llc | Base metal dehydrogenation of amine-boranes |
US7695704B2 (en) * | 2007-02-13 | 2010-04-13 | Gm Global Technology Operations, Inc. | Procedure for the hydrogenation of BNH-containing compounds |
WO2009072989A2 (en) * | 2007-12-05 | 2009-06-11 | National University Of Singapore | A hydrogen storage material and a process for release of hydrogen |
FR2930245B1 (en) | 2008-04-16 | 2010-09-17 | Snpe Materiaux Energetiques | SOLID HYDROGEN-GENERATING COMPOUNDS BY SELF-MAINTAINING COMBUSTION COMPRISING A POLYAMINOBORANE AND AT LEAST ONE INORGANIC OXIDANT; PROCESS FOR GENERATING HYDROGEN |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4801439A (en) | 1986-09-15 | 1989-01-31 | Sri International | Catalytic process for making compounds having a non-Lewis acid/base bond between a group IIIA metal and group VA nonmetal |
US6348179B1 (en) | 1999-05-19 | 2002-02-19 | University Of New Mexico | Spherical boron nitride process, system and product of manufacture |
US20050069488A1 (en) | 2003-09-30 | 2005-03-31 | Ji-Cheng Zhao | Hydrogen storage compositions and methods of manufacture thereof |
US20060099127A1 (en) * | 2002-06-25 | 2006-05-11 | Alicja Zaluska | New type of catalytic materials based on active metal-hydrogen-electronegative element complexes for hydrogen transfer |
US20060165577A1 (en) * | 2002-08-19 | 2006-07-27 | Seung-Hoon Jhi | Boron oxide and related compounds for hydrogen storage |
US20060194695A1 (en) * | 2004-08-27 | 2006-08-31 | Westinghouse Savannah River Co., Llc | Destabilized and catalyzed borohydrided for reversible hydrogen storage |
-
2005
- 2005-08-22 US US11/208,816 patent/US7361213B2/en not_active Expired - Fee Related
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4801439A (en) | 1986-09-15 | 1989-01-31 | Sri International | Catalytic process for making compounds having a non-Lewis acid/base bond between a group IIIA metal and group VA nonmetal |
US6348179B1 (en) | 1999-05-19 | 2002-02-19 | University Of New Mexico | Spherical boron nitride process, system and product of manufacture |
US20060099127A1 (en) * | 2002-06-25 | 2006-05-11 | Alicja Zaluska | New type of catalytic materials based on active metal-hydrogen-electronegative element complexes for hydrogen transfer |
US20060165577A1 (en) * | 2002-08-19 | 2006-07-27 | Seung-Hoon Jhi | Boron oxide and related compounds for hydrogen storage |
US20050069488A1 (en) | 2003-09-30 | 2005-03-31 | Ji-Cheng Zhao | Hydrogen storage compositions and methods of manufacture thereof |
US20060194695A1 (en) * | 2004-08-27 | 2006-08-31 | Westinghouse Savannah River Co., Llc | Destabilized and catalyzed borohydrided for reversible hydrogen storage |
Non-Patent Citations (2)
Title |
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C.A. Jaska, et al., "Transition Metal-Catalyzed Formation of Boron-Nitrogen Bonds: Catalytic Dehydrocoupling . . . ," 2003, J Am Chem Soc, pp. 9424-9434, vol. 125. |
C.K. Narula, et al., "Boron-Nitrogen Polymers/Boron Nitride System for Hydrogen Storage," Mar. 2005, pp. 34-36. |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8029602B1 (en) * | 2009-03-05 | 2011-10-04 | The United States Of America As Represented By The Secretary Of The Navy | Chemical hydrogen storage materials having guanidinium borohydride |
US20110008693A1 (en) * | 2009-07-08 | 2011-01-13 | Ford Motor Company | Hydrogen storage materials containing ammonia borane |
US8038980B2 (en) * | 2009-07-08 | 2011-10-18 | Ford Motor Company | Hydrogen storage materials containing ammonia borane |
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US20070039474A1 (en) | 2007-02-22 |
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